JPS60161936A - Production of alpha-(perfluoroalkyl) carbinol - Google Patents

Abstract

PURPOSE:To obtain the titled compound in an industrial scale in high yield, by reacting a perfluoroalkyl halide with an organic carbonyl compound in the presence of zinc using a nickel and/or palladium-based catalyst. CONSTITUTION:The objective compound of formula III can be produced economically in high yield in an industrial scale without using ultrasonic radiation, by reacting the compound of formula I (Rf is 1-20C perfluoroalkyl; X is halogen such as I, Br, etc.) with the compound of formula II (R is 1-12C aliphatic hydrocarbon residue such as alkyl, alkenyl, etc. or aromatic hydrocarbon residue such as phenyl, substituted phenyl, etc.) in the presence of zinc using a nickel and/or palladium-based catalyst, preferably the complex of formula IV-V, etc. The amounts of the compound of formula II, zinc and the catalyst are preferably 1-3mol, 1-2mol and 0.01-0.01mol per 1mol of the compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing α-(perfluoroalkyl)carbinol.

Be/L/fluoroalkyl halide in the presence of zinc,
By reacting with an organic carbonyl compound, α-(
It is known to produce perfluoroalkyl) carbinols. For example, dimethylformamide (DMF
) Carbinol was obtained as shown below by reacting trif/I/olomethyl iodide, zinc and benzaldehyde in a solvent under ultrasonic irradiation.

OFs Engineering + Os Hs OHODMF Ca Hs C
H(OR) CF mHowever, since this reaction is only possible with the aid of ultrasound, it can only be applied to small-scale reactions in units of numbers. Ultrasonic irradiation is impractical in industrial-scale implementation, and therefore no method has yet been found that allows the above-mentioned reaction to be carried out on a relatively large scale with good yields.

Recognizing the above problems, the inventors have developed α
After intensive research on a method for producing -(perfluoroalkyl)carbinol industrially, it was discovered that the above compound could be obtained in good yields without using ultrasound through the action of a certain type of catalyst. Ta. That is, the present invention provides such an advantageous production method, in which perfluoroalkyl hasside is prepared in the presence of zinc.
The present invention relates to a method for producing α-(bel7/I/o-furkyl)carbinol, which is characterized by reacting it with an organic carbonyl compound using a nickel and/or palladium catalyst.

The reaction of the present invention can be represented by the following general formula (1).

(However, in the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms. Alternatively, the aromatic hydrocarbon residue R1 such as a phenyl group or a phenyl group having a substituent is suitably an H atom, an alkyl group having 1 to 12 carbon atoms, or a perfluoroalkyl group having 1 to 8 carbon atoms, and the reaction The optimum molar ratio may be appropriately selected depending on the type of material.Reaction temperature, pressure, or time are not particularly limited, but approximately 0 to 50°C.
The reaction can be carried out at a temperature of , a pressure of autogenous pressure to normal pressure, and a reaction time of 5 minutes to 12 hours.

As a reaction solvent, dimethylformamide, dimethylsulfoxide, acetonitrile, sulfolane, N-methyl-2-pyrrolidone, N-Schif'ohexyl-2-pyrrolidone, hexamethylphosphortriamide, 1.3-dimethy/l/- Aprotic polar solvents such as 2-imidazolidinone are preferred. Particularly preferred is dimethylformamide.

The amount of solvent used is not particularly limited, but the starting material RfX
An appropriate amount is 1 to 10 times, preferably 3 to 5 times, based on weight parts. Also, the presence of zinc t+! , 1 to 2 mol per 1 mol of Rfx, and the amount of nickel or palladium catalyst used is o, ooi to 0 per 1-1 nil of Rfx.
,01 mol is suitable. Zinc is preferably in the form of fine powder, but may be in the form of lumps.

Nickel-based and palladium-based catalysts may be used alone or in the form of various salts. There are some preferred examples.

Next, examples of the present invention will be described in more detail.

In the following examples, the reaction products are NMR, G, C
, , or M,8- confirmed.

Example I Reaction between CJxBr and phcao 300 - Zn powder (90% purity, same hereinafter) 7.92f, (PhiP), Ni01z (1074
f, 150 dDMF (-class dimethy/L' ho/L/
Dry with Muamide, 4A Molecu 2-sieve, same below. ) and installed a magnetic stirrer. 18
After adding acPhOHO (18,79f), seal, cool to -78°C, let stand for 10 minutes, then evacuate, 15.131
tCFxBr (101,62 mmol) was condensed. Raise the angle to room temperature, open time at 16%, 2
A mild fever occurred 0 minutes later.

The ampoule was opened and poured into a 2N Hc1720-aqueous solution. After stirring, extract with ethyl ether at 400 oc, Na
Wash twice with H80m aqueous solution and twice with dilute hydrochloric acid. After drying the extract with ether over Mg80, the ether was removed on a rotary evaporator, and after distillation under reduced pressure, 7.93
2f (45.1 mmol) of α-)9 fluoromethylbenzyl alcohol was obtained. Yield 44.4%, ip,
84-87°C (14mmHg).

Example 2 Reaction of C3z”FsI with PhCHO 20d
15 d DMF and 27 t L in a round bottom 1 day flask
The Ph0HO7 flask was sealed with a rubber stopper and injected with CzFs. Zn of 0.97f and 0.0079f (Ph
il) zPdolg was added and reacted for 17 hours at room temperature. A severe exotherm was observed after 10 minutes. After the reaction 1
The contents were poured into 2N HCl, stirred, and extracted with ethyl ether. The extract was washed twice with 80 m NaH aqueous solution and twice with dilute hydrochloric acid, dried over MgeOa, and the ether was removed.

1.16P (5.1 mmol) of MMIkα-pentafluoroethylbenzyl alcohol was obtained under reduced pressure.

Yield 46%, b, p, 84-85℃ (10mmH
g).

Example 3 Reaction of 0FiBr and p-0ELOaHaOHO 1.01 Zn powder was placed in a 50 d glass pressure-resistant ampoule.
9P, (PhsP)2 Ni0120.011 f,
PhmP O, 0458ft, I)-01C! 6H40
HO2,484f and 15dDME' were added.

The ampoule was sealed, cooled to -780°C, left in the air for 10 minutes, and heated to 0FsBr 1.5t (10.07mm).
ol) was condensed. Let the ampoule rise to room temperature,
The reaction was allowed to proceed for 16 hours. After the reaction was completed, the contents were poured into 100 tons of 2N HCl, stirred, and extracted with ethyl ether. The extract was diluted twice with NaH80i aqueous solution and diluted HCl
The ether was removed by washing twice with water and drying with MgSO4. Distilled under reduced pressure to obtain 0.85 f (4.04 mmol) of α-trifluoromethyl parachlorobenzyl alcohol/
It's l/wo%. Yield i%, b, p, so℃ (4mmH
g).

Example 4 0zFs engineering and p-010! Reaction with aH40HO Zn powder 7,8 in 300ml glass pressure ampule
945 ts (Phs P)1 Ni O'lt
0.0432 t, PhmPo, 1985r, p-01
0sH40HO24,07S' and DMF150- were added, and a magnetic cooler was installed. Seal the ampoule, cool to -78°C, let stand for 10 minutes, then air out.
25.15 S' (102 mmol) of FlI was condensed. The ampoule was warmed to room temperature and reacted for 16 hours. After the reaction was completed, the contents were poured into 720 m/2N HCl, stirred, and extracted with ethyl ether. The extract was dried over Mg130* to remove ether. Furthermore, NaH8Os aqueous solution, 10% NazOOg
Washed once with water and twice with dilute HOI. Then Mg
The solvent was removed by drying at <50°C. Distilled under reduced pressure, 1
6.71i' (64.1 mmol) of α-(pentafluoroethyl)-halachlorobenzyl alcohol was obtained. Yield: 63cm, b, p.

82.5-84°C (4mmHg).

Claims (1)

[Claims] (1) α- characterized by reacting pepfluoroalkyl halide with an organic carbonyl compound in the presence of zinc using a nickel-based and/or palladium-based catalyst.
A method for producing (perfluoroalkyl N)carbinol.